TW200536152A - Phosphor and manufacturing method thereof, and light source, led using said phosphor - Google Patents

Abstract

Provided is a high-efficiency phosphor having an excitation band corresponding to the light in the ultraviolet-visible wavelength range (300 to 550 nm) emitted from a light emitting part which emits a blue color or ultraviolet light. A phosphor expressed by a composition formula of Ca0.985SiAlN3:Eu0.015 was obtained by preparing Ca nitride. Al nitride, Si nitride and Eu oxide, weighing the respective raw materials such that the molar ratio of the respective elements would be Ca:Al:Si:Eu=0.985:3:1:0.015, mixing the raw materials under a nitrogen atmosphere, and thereafter firing the obtained mixture in a nitrogen atmosphere at 1500 DEG C.

Description

200536152 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to phosphors used in display units such as CRT, PDP, FED, EL, fluorescent display tubes, LEDs, fluorescent lamps and other lighting units, and particularly The phosphor is suitable for use in LEDs, light sources, and lighting units that are equipped with light emitting parts such as ultraviolet and blue and emit visible light or white light. The present invention relates to the phosphor, a method for manufacturing the same, and the use of the phosphor Light source, LED. [Prior art]

It is known that by combining a blue or ultraviolet light emitting element with a phosphor having an excited band in the ultraviolet to blue wavelength region generated by the light emitting element, a white light emitting LED can be obtained as a representative Light source or lighting unit. It is known to use phosphors such as Y2〇2S: Eu, La2〇2S: Eu '3.5Mg0 · 0.5 Mg F 2 · Ge〇2: Mn, (La, Mn, Sm). ) 2〇2S · Ga2O3 was used as a red phosphor, ZnS: Cu, Al, SrAl2O4: Eu, 88 ^ 11, ^ 111 was used as a green phosphor, and the person was 〇: 〇6 Used as yellow phosphor, BAM: Eu, Sr5 (P〇 / i) 3Cl: Eu, ZnS: Ag, (Sr, Ca, Ba, Mg) i〇 (P〇4) 6Cl2: Eu used as blue Phosphor. Therefore, by combining these phosphors and the light emitting portion, a light source or lighting unit represented by a white or monochromatic LED can be obtained. Proposals for white LED phosphors include oxynitride glass phosphors (refer to Patent Document 1), phosphors based on silicon dragon (Sia 1 ο η) (refer to Patent Documents 2, 3), Nitrogen-containing phosphors such as silicon nitride (see Patent Documents 4 and 5), and a lighting device using such phosphors have been proposed. 5 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152 (Patent Document 1) Japanese Patent Laid-Open No. 2 0 0 1-2 1 4 1 6 2 (Patent Document 2) Japanese Patent Laid-open 2 0 0 3-3 3 6 0 5 9 (Patent Document 3) Japanese Patent Laid-Open No. 2 0 0 3-1 2 4 5 2 7 (Patent Document 4) Japanese Patent Special Table 2 0 0 3- 5 1 5 6 5 (Patent Document 5) Japanese Patent Laid-Open No. 2 0 3-2 7 7 7 4 6 [Summary of the Invention] (Problems to be Solved by the Invention)

Among the light sources represented by the above-mentioned combination of a light-emitting portion emitting blue or ultraviolet light and a phosphor having an excitation band in the ultraviolet to blue wavelength region light generated by the light-emitting portion, and emitting visible light and white light In order to improve the brightness of visible light or white light, in addition to the natural enhancement of the luminous efficiency of the light emitting part, there is a strong demand for improving the luminous efficiency of the phosphor. In the following, the phosphor will be described by taking an example of an LED that emits white light by a combination of a blue or ultraviolet light emitting element and a phosphor. When the phosphor is used for a white LED, the brightness of the white LED will also be improved with the improvement of the luminous efficiency of the phosphor. Therefore, a phosphor with better luminous efficiency is required for the luminous wavelength of the light-emitting element. For example, YAG: C e-based yellow phosphor, when the blue light of the LED light emitting element is used to emit light, it will fall within the excitation range with good efficiency, and good yellow light emission can be obtained, but when the ultraviolet of the LED light emitting element is used, When light is emitted, it will deviate from the excitation range, and high light emission cannot be obtained. In addition, related red phosphors have a poor luminous efficiency. Therefore, when mixing with other phosphors, a method of increasing the blending ratio of red phosphors to compensate for the amount of luminescence is adopted, but Efficiency is still required 6 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152 Better phosphor. The present invention is completed after considering the above-mentioned circumstances, and provides a light emitting element emitting light from blue or ultraviolet light, which emits light having an excitation band corresponding to light in a wavelength range of ultraviolet to visible (300 to 550 nm). High-efficiency phosphor, manufacturing method thereof, and light source using the phosphor. (Means for solving problems)

The inventors of the present invention conducted research on the matrix composition of various phosphors, and as a result, found that a phosphor with a novel matrix composition having higher efficiency and excellent light emission characteristics. The first purpose fluorescent system is represented by the composition formula MniAaBbNn: Zz; among the above phosphors, the M element is a valence element, the A element is a valence element, and the B element is a valence element. IV-valent element, N-based nitrogen, and Z-based system are active [[activat 〇r], (ni + z): a: b: n = 1: 1: 1: 3 o The second purpose fluorescent system As for the phosphor of the first purpose, the M element is at least one element selected from Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg; the A element is selected from B (boron), Al , Ga, In, Tl, Y, Sc, P, As, S b, Bi, select at least one element; element B is selected from Si, Ge, Sn, Ti, Hf, M0, W, Cr Among Pb, Zr, at least one element is selected; Z element is at least one element selected from rare earth elements or transition metal elements. 7 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152 The fluorescent system of the third purpose is any phosphor of the first or second purpose, in which A element is A 1, B element is S i. The phosphor system according to the fourth object is the phosphor according to any one of the first to third objects, wherein the matrix structure of the phosphor does not contain oxygen. The fluorescent system according to the fifth objective is the phosphor according to any one of the first to fourth objectives, wherein

Molar ratios of the M element and the activator Z element: z / (Hi + z), which are equal to or greater than 0.0001 and equal to or less than 0.5. The fluorescent system according to the sixth aspect The phosphor according to any one of the first to fifth aspects, wherein the M element is at least one element selected from Mg, Ca, Sr, Ba, and Zn. The fluorescent system according to the seventh aspect The phosphor according to any one of the first to sixth aspects, wherein the Z element is at least one element selected from Eu, Mn, and Ce. The fluorescent system according to the eighth aspect is the phosphor according to the seventh aspect, wherein the element Z is Eu. The fluorescent system according to the ninth aspect is the phosphor according to the eighth aspect, wherein the M element is Ca. The fluorescent system of the 10th objective 8 3 12XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152 The phosphor according to any of the first to ninth objectives, wherein the fluorescent system is in a powder form. The fluorescent system according to the eleventh aspect The phosphor according to the tenth aspect, wherein the average particle size of the phosphor is not more than 20 m and not more than 1 m. Fluorescent system of purpose 12 The phosphor according to any of purposes 1 to 11 contains:

When the relative intensity of the diffraction peak with the strongest intensity is set to 100% in the powder X-ray diffraction pattern formed by C ο α rays, the Bragg angle (20) of the X-ray diffraction spectrum (B raggang 1 e) In the range of 36.5 ° to 37.5 ° and 41.9 ° to 42.9 °, a phase with diffraction peaks with a relative intensity of 10 ° / 〇 or more is shown. . The fluorescent system of the 13th object is any one of the phosphors of the 1st to the 11th objects, and contains: When the powder X-ray diffraction pattern is formed by using C ο α rays, the diffraction peak with the strongest intensity is opposed to When the intensity is set to 100%, the Bragg angle (20) of the X-ray diffraction spectrum is 36.5 ° to 37.5 °, 41.9 ° to 42.9 °, and 5 6. In the range of 3 ° ~ 5 7 3 °, the phase with diffraction peaks with a relative intensity of 10% or more is the main phase. The fluorescent system of the 14th object is any one of the phosphors of the 1st to 11th objects, and contains: When the powder X-ray diffraction pattern is formed by using C ο α rays, the strongest diffraction peaks are opposed to each other. When the intensity is set to 100%, the Bragg angle (20) of the X-ray diffraction spectrum is 36.5 ° to 37.5 °, 9 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152 40.9 ° ~ 41 · 9. , 41.9. ~ 42.9. , 56.3. ~ 57 · 3. , 66.0. ~ 67.0. In the range of 75.8 ° ~ 76.8 ° and 81.0 ° ~ 83.0 °, the phase with diffraction peaks with a relative intensity of 10 ° / 〇 or more is displayed. The fluorescent system according to the 15th object The phosphor according to any one of the 12th to 14th objects, wherein the crystal of the above-mentioned generated phase is an orthorhombic orthorhombic crystal. The fluorescent system according to the sixteenth object is any one of the phosphors according to the first to eleventh objects, wherein

The carbon content is less than 0.08% by weight. The fluorescent system according to the 17th object The phosphor according to any one of the 1st to 11th objects, wherein the oxygen content is less than 3.0% by weight. The fluorescent system according to the eighteenth object The phosphor according to any one of the first to eleventh objects, wherein the carbon content is less than 0.8% by weight and the oxygen content is less than 3.0% by weight 〇

It has any one of the first to eighteenth phosphors and a light-emitting part that emits light of the first wavelength; a part of the light of the first wavelength is used as an excitation source, so that the phosphor is at a wavelength different from the wavelength of the first wavelength Glow. The light source of the 20th object is the light source of the 19th object, wherein the light emitting part emitting light of the first wavelength is the LED. 10 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152 The light source of the 21st purpose is the light source of the 19th or 20th purpose, wherein the first wavelength is 300nm ~ 550ηπ. The LED of the 22nd object has any one of the phosphors of the 1st to 18th objects and a light-emitting part that emits light of a first wavelength; a part of the light of the first wavelength is used as an excitation source, so that the phosphors are different The light is emitted at the wavelength of the first wavelength.

The LED of the 23rd mesh is the LED of the 22nd mesh, wherein the first wavelength is a wavelength of 300 nm to 550 nm. The method for producing a nitride phosphor according to the second objective is the method for producing a nitride phosphor according to any of the first to eighth objectives; the above-mentioned nitride phosphor raw material is filled in a boron nitride material and fired. A nitride phosphor is produced by firing in a container in an inactive environment. The method for producing a nitride phosphor according to the second 5th object is the method for producing a nitride phosphor according to the second 4th object, wherein the raw material of the nitride phosphor is at 1 2 0 ° C to 17 Baking is performed at a temperature of 0 0 ° C. The method for producing a nitride phosphor according to the 26th aspect is the method for producing a nitride phosphor according to the 24th or 25th aspect, in which the above-mentioned nitride phosphor raw materials are fired during the firing process. Firing is performed at a pressure of 0.5 MPa or less. (Effects of the Invention) 11 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848

200536152 In the 1st to 18th objects, the phosphors with the compositional formula MmAaBbNn: Zz (m + z): a: b: n = l: l: l: 3 are emitted from blue light emitting elements. Ultraviolet to blue (wavelength region 3 0 (L · has an excitation band and performs high-efficiency light emission. Therefore, by combining with the external ~ blue light emitting part, high-efficiency, high-brightness, or white LED or light source illumination can be obtained In addition, in the tenth purpose, because the nitride phosphor belongs to, coating or filling of the nitride phosphor can be easily performed. Φ 1 In the purpose, the average particle size of the powder of the nitride phosphor is as follows. Above 1 // m, the luminous efficiency will be improved. In addition, in the 12th to 15th objectives, because the fluorescence system emits light in the range of 580 ~ 680nm, it has the advantage of high luminous intensity, and in the ultraviolet ~ In the wide range of visible light wavelengths (300 ~ 550nm), it has a flat and high-efficiency excitation band. In addition, according to any of the phosphors in the 16th to 18th objectives, the carbon content is less than 0. 0 8% by weight of nitride phosphors and 3.0% by weight of nitride phosphors due to oxygen, because In either case, the content of impure carbon and oxygen impurities is relatively small, so it can suppress the reduction of the luminous intensity of the phosphor and improve the fluorescent efficiency of the nitride. Furthermore, in the 19th to 21st objectives, Any light source emits visible light by banding and emitting light in a predetermined wide wavelength region (300 to 550 nm) emitted by the fluorescent portion, so visible light can be obtained by the nitride phosphor and the light emitting portion. Or white light with high luminous efficiency light source 312XP / Fafa Invention Specification (Supplement) / 9106/94105848 and UV light -5 50 nm) light should emit a monochromatic powder in purple. In addition, the 2 # # m The light emission peak wavelength range of the light peak wave is because it has a smaller amount because it has a combination of excitation to the light emitting body of the nitride light emitting body, 12 200536152 Furthermore, the 22nd or 23rd LED, because nitrogen The compound phosphor has an excitation band and emits light in a predetermined wide wavelength region (300 to 5500 n in) emitted by the light emitting portion. Therefore, by combining the nitride phosphor and the light emitting portion, You can get visible or white light Luminous efficiency of LED.

Furthermore, according to the method for manufacturing a phosphor according to the 24th object, nitride phosphors are filled with a boron nitride material firing container and baked in an inactive environment to obtain nitride phosphors. Nitride phosphors with less carbon and oxygen impurities can be prepared. Accordingly, a nitride phosphor having fewer impurities that have no effect on light emission can be obtained, so that the decrease in the luminous intensity can be suppressed, and the luminous efficiency of the nitride phosphor can be improved. Furthermore, according to the method for manufacturing a phosphor according to the 25th or 26th objective, a nitride phosphor that suppresses the decrease in luminous intensity and improves the luminous efficiency of the nitride phosphor can be produced with high productivity. [Embodiment] (Fluorescent structure and optical characteristics of the present invention) The fluorescent system of the present invention has a composition formula M m A a B b N n: Z z, and (m + z): a: b : n = l: l: l: 3 The quaternary parent structure phosphors. Among them, the M element is an element having a valence number in the above-mentioned phosphor. The element A is an element having a valence of 1 to 2 in the phosphor. The B element is an element having a valence of I to V in the phosphor. N is nitrogen. The element Z functions as an activator in the phosphor. If the phosphor has this matrix structure, it will become a phosphor with high luminous efficiency. Furthermore, if the mother structure of the above-mentioned phosphor adopts a chemically stable structure, it is difficult to generate an uneven phase, so the luminous efficiency will not be reduced. This is the best structure. 94105848 200536152 structure. Here, the structure of the phosphor is capable of forming a chemically stable structure. It is best to set the above phosphor to be (m + z) when expressed by the compositional formula MmAaBbNn: Zz: a: b: η = 2 : 1: 1: 3. The reason is that the element M is a valence, the element A is a valence, and the element B is a valence, and it is combined with a valence nitrogen to form a stable nitrogen compound. However, it can be judged that several compositional deviations will be caused. Here, since the valent metal nitride usually forms the chemical formula of M 3 N 2, the m valent metal nitride system forms the chemical formula of AN, and the IV valent metal nitride system forms the chemical formula of φ into B 3 N 4, so we are making such a formula. In the state of M: A: B2: 1: 1, it is only necessary to mix each nitride raw material with an Emol ratio of 1: 3: 1. However, when the Z element is used as a valence element as an activator, it will form (m + z): a: b: η = 1: 1: 1: 30 because it replaces part of the M element. By forming a chemically stable structure, it is judged that a high-efficiency and high-brightness phosphor will be obtained.

The M element is preferably at least one element selected from Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg. In other words, the M element may be alone, such as Ca, or a mixture of Ca, Mg, ... and the like. The A element is preferably at least one element selected from B (Shi Peng), Al, Ga, In, Tl, Y, Sc, P, As, Sb, and Bi. In other words, the A element may be alone such as A 1 or a mixture of A 1, G a,... The B element is preferably at least one element selected from Si, Ge, Sn, Ti, Hf, Mo, W, Cr, Pb, and Zr. In other words, the B element may be alone, such as Si, or a mixture of Si, Ge, ... and the like. 14 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152 Z element is preferably at least one element selected from rare earth elements or transition metal elements. In other words, the Z element may be alone, such as Eu, or a mixture of Eu, La, ... and the like. By forming the M element, A element, B element, and Z element as described above, the luminous efficiency of the phosphor can be further improved.

When the A element is A 1 and the B element is S i, the respective nitrides are generally used for a heat transfer material or a structural material, which are easily available and inexpensive. In addition, it is easy to reduce the environmental load. Therefore, by selecting these elements as raw materials, inexpensive and easy-to-use phosphors can be obtained, which is an optimal configuration. According to the phosphor of the present invention, it is represented by the composition formula MmAaBbNn: Zz and (m + z): a: b: η = 1: 1: 1: 3 Yu Yu is familiar with the composition system of a silicon dragon matrix (S i-ΑΟ0-Ν system) phosphor, and a phosphor having a Si-0-N system matrix. According to the study by the present inventors, it has been found that if the content of oxygen in the phosphor is too large, the luminous efficiency will decrease, and the phosphor's emission wavelength will tend to shift toward the short wavelength side. From this viewpoint, the phosphor of the present invention, which does not contain oxygen in the constituent elements of the matrix, not only has high luminous efficiency, but also prevents the emission wavelength from shifting toward the short-wavelength side, which is the optimal composition. In the phosphor of the present invention, the molar ratio z / (m + ζ) of the M element to the activator Z element is preferably in the range of 0.0001 or more and 0.5 or less. If the molar ratio z / (m + ζ) of the M element and the activator Z element is within this range, it can avoid the situation that the derivative concentration is extinction due to the excessive content of the activator, which leads to the reduction of the luminous efficiency, and vice versa. Avoiding too few derivatized light-emitting atoms due to too little activator content, leading to a decrease in luminous efficiency. Depending on the type of activating element Z added, although the most appropriate ratio of z / (m + ζ) is 15 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848

200536152 There are several differences, but it is best to have a range of 0.0005 or more and 0.1 or less to obtain good light emission. If the M element of the phosphor of the present invention belongs to at least one element selected from Mg, Ca, Sr, and Ba, it belongs to an optimal structure with low raw material load and easy environmental load. If the element Z of the phosphor of the present invention belongs to at least one element selected from Eu, Mn, and Ce, the luminous efficacy of the phosphor will be improved and it will be an optimal composition. If the Z element of the phosphor of the present invention is Eu, since the emission wavelength will be the color wavelength, a white phosphor with excellent luminous efficiency can be obtained, which belongs to the best structure. If the M element of the phosphor of the present invention is Ca, the A element is A1, the B element Si, and the Z element is Eu, since the raw material can be easily obtained and the light emitting wavelength of the phosphor with a small environmental load shows a red wavelength, it will be possible to A red phosphor for a white light-emitting unit with good luminescence is obtained, which belongs to the best composition. When the phosphor of the present invention is a powder, the average particle size of the powder is at most 20 # m. The reason is that it is judged that the luminescence of the phosphor powder mainly occurs on the surface. If the average particle diameter exceeds 20 // m, the average surface area of the phosphor powder will be reduced. In addition, according to discussions by the present inventors, when the average particle diameter is less than 1 // m, the luminous efficiency will also decrease. Therefore, the average particle size of this phosphor powder is less than 20 / m and more than 1 / zm. In addition, if the phosphor powder is considered to be used as a phosphor for LEDs, the phosphor powder is mixed with a resin and applied to the 312XP / Fafa Invention Specification (Supplement) / 94- 06/94105 848

Within 1, Zn and ring, the yield is shown as red-red pigment. The efficiency is better than the weight of the particles. When the best body powder LED 16 200536152 is invented, the average particle size is the most from the viewpoint of obtaining good coating properties. Fortunately, it is below 20 m and above 1 // m. By combining the phosphor obtained by the present invention with a light source such as blue or ultraviolet light emission, a high-efficiency light source of visible light monochrome or white can be obtained. The phosphor obtained by the present invention will receive light in a wide excitation range of 300 to 550 nm and emit light. Therefore, by combining a blue or ultraviolet light source, a monochromatic or white visible light can be obtained. High efficiency light source.

By combining the phosphor obtained in the present invention with, for example, a blue or ultraviolet light emitting LED light emitting portion, a high-efficiency LED can be obtained in monochromatic or white light. Since the phosphor obtained by the present invention will receive light in a wide excitation range of 300 to 550 nm and emit light, by combining blue or ultraviolet light emitting LED light emitting parts, a monochromatic or visible light can be produced. White high efficiency LED. (X-ray diffraction spectrum of phosphor powder of the present invention) Next, the powder X-ray diffraction pattern displayed by the phosphor of the present invention will be described with reference to Figs. 1 (A) and (B). FIG. 1 (A) shows an example of the phosphor of the present invention. It is a powder X-ray diffraction pattern formed by the phosphor of C ο α rays in Example 1 described later. FIG. 1 (B) shows the X-ray. The diffraction pattern is compared with the spikes of the JCPDS card. Among them, the spike data occupying the upper half in FIG. 1 (B) represents the Bragg angle (20) and intensity of the main spikes shown in FIG. 1 (A) according to the linear position and height. Secondly, the cardinal bee that occupies the lower part is the Bragg angle (20) and the intensity of the main peaks of the crystals recorded in the J C P DS card, which are expressed in terms of linear position and height. (Among them, for the sake of comparison of mitral peaks, the peak intensity of the C A A 1 S 1 N 3 crystal is shown upside down.) 17 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152

From the comparison of the mitral peaks shown in FIG. 1 (B), it is known that the phosphors of the present invention are similar to the C a A 1 S 1 N 3 crystals recorded in the JCPDS card. Although the overall pattern of the main peaks is similar, if you look at it in detail, It will be found that the peaks of the phosphor of the present invention are all shifted toward a direction in which the Bragg angle (20) becomes smaller. Although the two are similar, they have crystal structures with different crystal plane intervals. Among them, the factors that cause the difference in the crystal structure of the two can be considered to use Ca 0, A 1 N, and Si 3 N 4 as the Ca A 丨 S i N 3 series raw materials recorded in the JCPDS card. In contrast, because the present invention The light system uses nitride raw materials related to Ca 3 N 2, A 1 N, Si N 4 and the elements constituting the parent structure, so the crystal structure of the two has a difference in the amount of oxygen present in the structure, and In the case of the phosphor of the present invention, part of Ca will be replaced by Eu and the like. In particular, the overall pattern of the main peaks is similar, which means that the formation phase of the phosphor of the present invention can be judged, and it also has the same orthorhombic crystal as the C a A 1 S i N 3 crystal described in the J C P D S card. From the above phenomenon, the present inventors judge the present invention. Although the phosphor of the invention is similar to the Ca A 1 S i N 3 crystal described in the JCPDS card, it has a novel crystal structure, and the phosphor of the present invention having the novel crystal structure The structure of the light body is regulated using the X-ray diffraction pattern shown by the phosphor. Here, the main peaks in the X-ray diffraction pattern of the generated phase contained in the phosphor of the present invention will be described. It is apparent from FIG. 1 (A) that the generated phases contained in the phosphor of the present invention are at Bragg angles (20) of 36.5 ° to 37.5 °, 40.9 ° to 41.9 °, 41.9 ° to 42.9 °, 56 · 3. ~ 57. 3. , 66. ◦. ~ 67.0. , 75.8. ~ 76, 8. And 81 · 0. There are characteristic spikes in the range of ~ 8 3 °, among which the peaks in the range of 36.5 ° ~ 37.5 °, 41.9 ° ~ 42.9 ° are particularly strong, 5 6.3 ° ~ 18 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152 5 7.3 Spikes in the range of 3 ° are inferior to their characteristic spikes. These spikes belong to diffraction spikes having a relative intensity of more than 10% when the relative intensity of the diffraction peak with the strongest intensity in the X-ray diffraction pattern is set to 100%. Furthermore, if these peaks are viewed from the perspective of the half-value width of the diffraction pattern, the half-value width will be all below 0.25 ° to obtain sharp diffraction peaks. This sharp diffraction peak system shows a structure having a non-amorphous structure and a superior crystallinity.

Although the detailed correlation between the above-mentioned X-ray diffraction pattern characteristics exhibited by the phosphor of the present invention and the characteristics having excellent light emission characteristics and good excitation band characteristics has not been clarified, it may be considered as follows. First, in the X-ray diffraction pattern, it is judged that the peak pattern of the target generated phase can be obtained by a single phase, which will be closely related to the case where the phosphor of the present invention has excellent light emission characteristics and good excitation band characteristics. Among them, in this X-ray diffraction pattern, the phenomenon of peaks of the raw materials (C a 3 N 2, A 1 N, Si 3 N 4, and Eu 2 0 3) used in making the phosphor was not found. The results of the target generation phase are obtained by single phase. That is, when the phosphor is manufactured, if the firing temperature is insufficient and the amount of raw materials is not appropriate, in the fired phosphor, in addition to the target formation phase, there will be an excess of the above raw materials, causing the excitation light to be irradiated. The average amount of phosphor per unit area is reduced, and the excess material will absorb the excitation light or emitted light, so the luminous efficiency of the phosphor will be reduced, and superior luminous characteristics will not be obtained. Therefore, the characteristics of the above-mentioned peaks of the raw materials were not found in the X-ray diffraction pattern, and it can be considered that the phosphor indicating the measurement object will have superior light emission characteristics and a good excitation band. In addition, the intensity of the X-ray diffraction peak intensity can be considered to reflect the crystallinity of the phase of 19 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94] 05848 200536152. Therefore, in the case where the crystallinity of the generated phase is high, it can be considered that a structure that emits light around Eu 2 + in the generated phase will be formed, and by continuously and regularly forming this structure, excellent light emitting characteristics can be obtained. In contrast, the intensity of X-ray diffraction peaks is weak, so it is judged that the crystallinity is low. In this case, because the Eu2 + surrounding structure of the luminous center is not regular enough, the distance between Eu2 and Eu2 + will be too close, which will cause the In the case of concentration extinction, and there is no Eu2 + entry on one side where Eu2 + should enter, it should be judged that superior luminescence characteristics will not be obtained.

Finally, the Bragg angle (20) is 3 8 ~ 4 (the spikes appearing near Γ are weak, it is best not to find any spikes that may appear near the right side of the spike (but these spikes will overlap, in interpretation) It must be noted) that it can be judged that it will reflect the characteristics of excellent luminescence and good excitation band. This phenomenon can be judged that the peaks that appear near the Bragg angle (20) 3 8 ~ 4 0 ° belong to the phosphor raw materials. A1N spike overlaps with CaAlSiN3: Eu intrinsic spike. That is, as mentioned above, it is aimed at the production of phosphors, if the firing temperature is not enough and the amount of raw materials is not appropriate, excess raw materials will remain in the phosphors after firing. It will explain the phenomena that affect the luminous characteristics. If A 1 N remains, because the A 1 N is gray, it will absorb the light emitted by the phosphor sample or the light of the excitation light. It should be judged that it will be directly related to the luminescence. Intensity reduction phenomenon. Therefore, in order to obtain a phosphor with a strong luminous intensity, it is preferable that the intensity of the A 1 N diffraction peak around 3 8 to 4 0e is weak, so it can be judged that the mitral peak overlaps 3 8 to 4 0 nearby The spikes that appear are relatively weak, especially the A 1 Ν spikes that may be best located near the right side of the Ca A 1 S i Ν 3: E u intrinsic spikes are completely undiscovered. 20 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152 The method of measuring the powder X-ray diffraction pattern of the phosphor of the present invention will be described here. The measured fluorescence system is pulverized into a predetermined size by a pulverizing means such as a ball mill after firing. (Preferably 2 0 // m ~ 1 // m), average particle diameter, and then load it into the sample support frame to make the upper end flat, and use "RINT 2 0 0 0" manufactured by Rigaku Electric Co., Ltd. of XRD device Measurement. The measurement conditions are as follows: Measuring machine used: "RINT 2 0 0 0" manufactured by Rigaku Corporation

X-ray tube: C ο κ α Tube voltage: 40 k V Tube current: 30 m A Scanning method: 2 0/0 Scanning speed: 0. 0 3 ° / mi η Sampling interval: from 0. 0 1 ° Start angle (20): 10 ° Stop angle (20): 90 ° Furthermore, the related Bragg angle (20) shift phenomenon can be judged because the sample surface irradiated by X-rays is not flat, X The radiographic measurement conditions (especially the scanning speed) are different and shifts occur. Therefore, the range in which the diffraction peaks of the above-mentioned features can appear will also have some offsets, and this phenomenon can be considered to be tolerated. In this specification, in order to suppress this shift phenomenon as much as possible, S i is mixed with a phosphor sample under the condition that the scanning speed is set to 0.3 ° / mi η, and the X-ray measurement is performed. Post-correction of the S i sharp offset to obtain the Bragg angle (2 Θ). 21 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152 (Method for Producing the Fluorescent Phosphor of the Present Invention) Here, for the example of the method for producing the red phosphor of the present invention, the composition formula CaAlSiN3: Eu The production of a phosphor represented by (Eu / (Ca + Eu) = 0.020) will be described as an example. Although the raw materials of the respective nitrides of the elements M, A, and B may be commercially available materials, since the higher the purity, the better, it is better to prepare 2N or more, especially 3N or more. In general, the particle diameter of each raw material particle is preferably a fine particle from the viewpoint of promoting the reaction, but the particle size and shape of the phosphor obtained will vary depending on the particle diameter and shape of the raw material. Therefore, it is only necessary to prepare a nitride raw material having an approximate particle size in accordance with the particle size required for the phosphor finally obtained. The raw material of the Z element is preferably a commercially available nitride raw material or a metal monomer, but since the amount of addition is small, there is no problem even if an oxide is used. However, the higher the purity, the better. It is better to prepare 2N or more, especially 3N or more. If C a is manufactured. · 〇 8. A 1 S i N 3: E u. ·. 2. If, for example, nitrides of element M, element A, and element B, Ca 3 N 2 (2 N), A 1 N (3 N),

S i 3 N 4 (3 N), and the element Z is prepared as Eu 2 0 3 (3 N). According to the molar ratio of the raw materials, Ca a: A 1: S i: E u = 0.98 0: 1: 1: 0. 0 2 0, and the raw material mixing ratio was weighed to obtain Ca3N2: 0.980 / 3mol, AlN: lmol, SisN ^ l / 3 m ο 1, Eu 2 0 3: 0.0 2 0/2 m ο 1 and mixed. For weighing and mixing, Ca 3 Ν 2 is more easily oxidized, so it is more suitable to operate in a glove box in an inactive environment. In addition, since the nitride of each raw material element is easily affected by moisture, it is preferable to use a gas that has been sufficiently removed from the inert gas. The mixing method can be either wet or dry. However, if 22 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152 uses pure water as a solvent for wet mixing, the raw materials will be decomposed. Therefore, an appropriate organic solvent must be selected. As the apparatus, a conventional apparatus such as a ball mill or a mortar can be used.

Put the mixed powder raw materials into the crucible, in a non-reactive environment such as nitrogen, at 100 0 T: above (preferably above 120 ° C, especially above 15 0 ° C) ) And heating is performed at a temperature of 1700 ° C or lower, and it is held for 30 minutes or more (preferably 3 hours) for firing. This is because the higher the sintering temperature, the faster the sintering will be performed, and the time can be shortened. In addition, even when the sintering temperature is low, the target light-emitting characteristics can be obtained by maintaining the temperature for a long time. However, longer sintering time will promote particle growth and increase the particle size. Therefore, it is better to set the sintering time in accordance with the target particle size. The pressure during firing in an inactive environment is preferably fired at 0.5 MPa or less (preferably 0.1 MPa or less). The reason is that if firing is performed at a pressure higher than this, sintering between particles will proceed excessively, which will be disadvantageous for pulverization after firing. Moreover, crucibles can be used with high purity without impurities, such as A 1 2 0 3 crucible, S i 3 N 4 crucible, A 1 N crucible, silicon dragon crucible, C (carbon) crucible, BN (Boron nitride) Crucibles that can be used in an inactive environment, such as crucibles, but BN crucibles are preferred because impurities from the crucible can be avoided. After the firing is completed, the fired product is taken out from the crucible and pulverized to a predetermined average particle size using a pulverizing means such as a mortar or a ball mill to obtain a composition formula C a. . 9 8. A 1 S i N 3: E u ◦. 〇 2 〇 phosphor shown. Among them, when Eu 2 0 3 is used as the Eu raw material, Ca 9.898AlSiO〇.〇3N2.9 (i: Eu〇.02 () Because the amount of oxygen is a small amount, there is no special problem with 23 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152. In addition, when you want to reduce the amount of oxygen more, as long as the Eu material is used E u metal or Eu nitride may be sufficient. (Reduction of impurities in the production of the phosphor of the present invention) The carbon content of the impurities in the fluorescent system of the present invention is less than 0.8% by weight, and the oxygen content of the impurities is Less than 3.0% by weight. It is desirable to satisfy both the carbon content of the impurities less than 0.8% by weight and the oxygen content of the impurities less than 3.0% by weight, but only one of them can be satisfied.

Whether it is a phosphor with an impure carbon content of less than 0.8% by weight, or a phosphor with an impure oxygen content of less than 3.0% by weight, because the content of carbon and oxygen impurities that have no effect on light emission is relatively small. When the light emission intensity is expressed in terms of relative intensity, the decrease of the light emission intensity by about 25 to 30% can be avoided, so the light emission efficiency can be improved. The method for manufacturing an impure substance-reducing phosphor according to the present invention is to fill a phosphor raw material in a firing container made of boron nitride and then fire it in an inactive environment to obtain a phosphor. With regard to this manufacturing method for reducing the impurity phosphor, a manufacturing example in which the phosphor is CaAlSiN3: Eu (where Ei ^ (Ca + Eu) Molar ratio = 0.05) is described. First, Ca, A1, and Si nitrides of the raw materials are prepared as C3N2 (2N), A1N (3N), and Si3N4 (3N), respectively. For E u raw materials, E u 2 0 3 (3 N) is prepared. The raw materials are weighed and mixed in such a manner that the molar ratio of each element is Ca: Al: Si: Eu = 0.985: 1: 1: 0. 0 1 5 ((C a + E u): A 1 : S i: = 1: 1: 1). This mixing can be carried out by a common mixing method such as a mortar, but it is preferable to operate in a glove box under an inert environment such as nitrogen. 24 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152

The reason for operating this mixture in a glove box in an inactive environment is that if this operation is performed in the atmosphere, the ratio of the oxygen concentration in the constituent elements of the matrix will collapse due to the oxidation or decomposition of the above raw materials. In addition to the possibility of reducing the light emitting characteristics, the composition of the phosphor target may deviate. In addition, since the nitride of each raw material element is easily affected by moisture, it is preferable to use a gas which sufficiently removes moisture. When a nitride raw material is used for each raw material element, in order to avoid decomposition of the raw material, a dry mixing method is preferably used, and a normal dry mixing method such as a ball mill or mortar can also be adopted. The powdered raw materials after mixing are filled in a crucible made of boron nitride in a firing container, for example, in a non-reactive environment such as a nitrogen environment with a pressure of 0.05 MPa, at 15 ° C / mi η. The temperature rise rate was increased to 15 0 ° C, and then held at 15 0 ° C for 3 hours to perform firing. Here, the present inventors have found that when a firing container (for example, a crucible) for firing phosphor raw materials is fired using, for example, a carbon firing container, impure carbon is mixed from the carbon firing container into the firing. The resulting phosphor may reduce the luminous intensity of the phosphor. According to the investigation by the present inventors, it has been found that if the amount of carbon contained in the phosphor reaches 0.8 wt% or more, the luminous intensity of the phosphor will start to decrease. In addition, the present inventors have discovered that when an alumina firing container is used for firing, oxygen from impurities is diffused from the alumina firing container to the fired phosphor, which may cause the phosphor to emit light. reduce. According to discussions by the inventors, it was found that when the amount of oxygen contained in the phosphor reaches 3.0 weight V or more, the luminous intensity of the phosphor starts to decrease. Therefore, the present inventors have found that by using a firing container made of boron nitride to perform 25 312XP / Fafa Invention Instructions (Supplement) / 94-06 / 94105848 200536152, the firing of the phosphor can be obtained. Phosphors with less effective carbon content of impurities and less oxygen content of impurities can suppress the decrease in luminous intensity and can improve the luminous efficiency of the luminous body. Therefore, the firing container is a boron nitride firing container. After the firing is completed, it is cooled from 15 0 ° C to 200 ° C in 1 hour, and then cooled to room temperature, and then used. Grinding means such as mortar and ball mill are pulverized to a predetermined (preferably 2 0 // m ~ 1 μm) average particle size, and the composition formula can be obtained.

Ca〇.985SiAlN3: Eu〇.〇i5 phosphor.

When the setting of E u / (C a + E u) is different, it can also be obtained by using the same composition method with the formulation amount of each raw material when filling and using the same manufacturing method. A phosphor of a predetermined composition. The phosphors obtained are all phosphors having a carbon content of less than 0.8% by weight and an oxygen content of less than 3.0% by weight. The fluorescent system of the present invention is formed into a powder in consideration of the ease of coating or filling. In this case, the average particle diameter of the fluorescent powder is preferably 20 / m or less. This reason is that the luminescence of the phosphor powder mainly occurs on the particle surface. Therefore, if the average particle size is set to less than 20 μm, the surface area per unit weight of the powder can be ensured, and the decrease in brightness can be avoided. Furthermore, if the powder is formed into a paste, the density of the powder can also be increased when coating the light-emitting element or the like, and from this viewpoint, a decrease in brightness can also be avoided. In addition, according to the investigation by the present inventors, although the detailed reason is not clear, from the viewpoint of the luminous efficiency of the phosphor powder, it is known that the average particle diameter is preferably larger than 1 W m. Based on the above, the average particle diameter of the phosphor powder of the present invention is preferably 1 // ηm or more and 20 β m or less. 26 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152 The phosphor of the present invention which is formed into a powder form is combined with a light-emitting portion by a well-known method (particularly in the light-emitting wavelength region 3 0 0 ~ 5 5 A light-emitting portion that emits light at 0 nm) has an excitation band and emits light in a wide-range wavelength region of light emitted by the light-emitting portion, so that a high light-emitting efficiency light source that emits visible light or white light can be obtained. In particular, a well-known method is used in which the light-emitting portion is combined with LEDs that can emit light in a wavelength range of 300 to 5500 nm, and a high-efficiency light source or LED that emits visible light or white light can be obtained.

Therefore, this light source (LED) can be used as various light sources for lighting devices such as display devices and fluorescent lamps. (Examples) Hereinafter, the present invention will be described more specifically based on examples. (Example 1) Commercially available Ca3N2 (2N), A1N (3N), Si3N4 (3N), Eu2〇3 (3N), and the molar ratio of each element was Ca: Al: Si: Eu = 0.985: 1 : 1: 0.015 to weigh each raw material, and use a mortar to mix in a glove box under a nitrogen environment. The mixed powder raw materials were heated to 15 0 ° C at a temperature increase rate of 15 ° C / mi η in a nitrogen environment at a pressure of 0.05 MPa, and were heated at 15 0 ° C. After firing for 3 hours, the composition was cooled from 15 ° C. to 200 ° C. within one hour to obtain the composition formula C a. . 9 8 5 S i A 1 N 3: E u 〇. !! 5 phosphors. Table 1 shows the analysis results of the obtained phosphor powder. The average particle diameter (D 50) of the obtained phosphor was 4.6 5 // m, the specific surface area was 1.1 3 m 2 / g, and the oxygen content of the impurities was 2.2 ° / 〇. 27 312XP / Fafa Invention Specification (Supplement) / 94-06 / 94105848 200536152 [Table 1]

Ca (° / 〇) Al (%) Si (%) N (° / 〇) Eu (° / 〇) 〇 (%) Other average particle size (D50) Specific surface area Ca 985AIS1N3: Eu 0.15 27.3 20.5 19.2 29.2 1.46 2.2 0. 1 4. 65 // m 1. 13m2 / g Next, measure the emission spectrum and excitation spectrum of the phosphor of the present invention. The measurement results will be described with reference to Figs. 7 and 8. 7 and 8 are the light emission intensities of the phosphors of the present invention on the vertical axis and the wavelength of light.

First, the emission spectrum of the phosphor of the present invention will be described with reference to Fig. 7. The so-called "luminous spectrum" refers to the spectrum released by an object when light or energy of a certain wavelength is irradiated to the object. As shown in Fig. 7, when the phosphor of the present invention is irradiated with monochromatic light of 450 nm, The wavelength spectrum of light emitted from a phosphor. It is obvious from FIG. 7 that the present fluorescent system will emit light in a wide wavelength region from 550 nm to 800 nm, and the highest emission is at 656 nm. In addition, the color of red light emission was visually recognized. Next, the excitation spectrum of the phosphor of the present invention will be described using Fig. 8. The "excitation spectrum" refers to the use of monochromatic light of various wavelengths to excite the phosphor of the object to be measured, and to measure the luminous intensity of a certain wavelength of light emitted by the phosphor, and the excitation wavelength dependence of this luminous intensity is measured. In this measurement, monochromatic light ranging from 250 nm to 5700 nm was irradiated to the phosphor of the present invention, and the excitation dependence of the luminous intensity at the wavelength of the phosphor's emission wavelength of 6 56 nm was measured. It is obvious from FIG. 8 that the excitation spectrum of the present phosphor is a wide range from around 300 nm to 6 0 η η], and the excitation band from around 300 nm to 600 nm In a wide range, high red light emission is displayed. (Example 2) 28 312XP / Invention Specification (Supplement) / 94-06 / 94] 05848 200536152 In Example 2, the fluorescent lamp of the present invention having a C a ,,, S i A 1 N 3: E uz composition formula is used. Light body, measuring the luminous intensity produced by the Z element concentration of the active material. For the production of measurement samples, the concentration of activator Eu was adjusted so that the relationship between Ca and m was z + 1, and the amounts of Ca and Eu were adjusted. This measurement result will be described with reference to FIG. 9. Among them, the vertical axis of Fig. 9 is the luminous intensity of the phosphor of the present invention, and the horizontal axis is the blending ratio of Ca and Eu Eu / (Eu + Ca) 値. In addition, in terms of light emission intensity, the light emission intensity when Eu / (Eu + Ca) = 0.015 was set to 100%. Then, the results of the adjustment of Eu μM E u + Ca) 値 φ between 0. 0 0 1 5 to 0. 06 are shown. The excitation system uses light having a wavelength of 450 nm. It is known from the results of FIG. 9 that at the beginning, the luminous intensity will increase with the increase of Eu / (Eu + Ca) 値, but a sharp point appears around 0.015, and then the luminous intensity gradually decreases. This phenomenon can be judged because the activator element will be insufficient in the part below 0. 015, and the concentration extinction will occur due to the activator element in the part above 0. 15 .

In addition to this luminous intensity measurement, the luminous chromaticity (X, Y) is also measured. The results are shown in Table 2. From the results in Table 2, it was confirmed that as the Eu / (Eu + Ca) 値 increases, the peak wavelength also shifts toward the long wavelength side. [Table 2] E X: 4 5 0 n m

Eu concentration spike intensity peak wavelength X y Ca0. 9975 A 1 S i N3: Eu0. 0015 0. 0015 28. 8% 632. 7 0. 608 0. 384 Ca0. 9925 A1S i N3: Euo. 0075 0.0075 75.5 ° / 〇644.3 0.651 0. 346 Ca〇.985AlSiN3: Euo.ois 0.0150 100. 0% 651. 3 0.671 0. 327 Ca〇. 97A1S i N3: Eu〇. 03 0.0300 77. 0 ° / 〇660 0 0. 683 0.315 Ca〇. 丨 A1S i N3: Eu〇_ og 0. 0600 54. l ° / 〇670. 2 0. 691 0. 306 29 312XP / Invention Specification (Supplement) / 94-06 / 94105848 200536152 (Example 3) On a nitride semiconductor LED whose light-emitting part emits ultraviolet light with a wavelength of 40.5 nm, a phosphor obtained by mixing the present invention and a commercially available blue phosphor (BAM) : Eu), a green phosphor (ZnS: Cu, Al), and causes the ultraviolet LED to emit light. In this way, each phosphor emits light using the light emitted by the LED as an excitation source, and a white LED can be obtained by mixing the colors of the phosphors' emission colors. In addition, by changing the mixing ratio of the phosphors, LEDs of various colors can be obtained.

Furthermore, a blue LED having a nitride semiconductor as a light emitting portion is coated with the phosphor obtained in the present invention and a commercially available yellow phosphor (Y A G.. C e), and the blue LED is caused to emit light. As a result, each phosphor will emit light using the light from the LED, and a reddish red LED with a low visual color temperature can be obtained. (Example 4) In Example 4, the phosphor of the present invention was compared with the CazSisNsiEu phosphor disclosed in Patent Documents 4 and 5. In addition, the Ca 2 S i 5 N 8: E u phosphor used in this example is a 2 N or 3 N reagent for Ca 3 N 2, Si 3 N 4, and Eu 2 0 3 As raw materials, the scales were weighed according to the methods of Ca, Si, and Eu at 1.97: 5: 0.03, and mixed in a mortar in a glove box under a nitrogen environment. The mixed powdered raw materials were calcined in a nitrogen atmosphere at a pressure of 0.05 MPa for 3 hours at 1 500 ° C, and then cooled and crushed as in Example 1 to obtain a composition formula C a 1. 9 7 S i 5 N 8: EU 0. 0 3 phosphor. The composition formula C a of the present invention obtained in Example 1 is obtained. . 9 8 5 S i A 1 N 3: E u. ◦ 丨 5 phosphors and the composition formula C a. 9 7 S i 5 N 8: EU 0. 0 3 Analysis results of phosphors, 30 312XP / Invention Specification (Supplement) / 94-06 / 94105848 200536152 is summarized in Table 3. From the results in Table 3, it can be seen that the impurities contained in the produced two phosphors have the same levels of oxygen and other elements, and the specific surface area of the two phosphors is also the same.

31 312XP / Invention Specification (Supplement) / 94-06 / 94105848 200536152 [Table 3]

Ca (° / 〇) Al (° / 〇) Si (° / 〇) N (° / 〇) Eu (%) 〇 (%) Other average particle size (D50) Specific surface area Ca〇.985AlSiN3: Eu〇.〇 is 27.3 20. 5 19. 2 29.2 1.46 2.2 0. 1 4. 65 // m 1. 13 m2 / g Cai. 97S i 5N8: Eu〇. 03 22.3 0 · 3 39. 6 34.2 1. 34 2. 1 0.2 4. 77 // m 1. 11 m2 / g Secondly, the emission spectra of the two phosphors are measured and compared in the same manner as in Example 1. Among them, the irradiated light is a monochromatic light of 460 nm. The results are shown in Figure 10 and Table 4. The diagram shown in FIG. 10 is the same as that in FIG. 7. The light emission spectrum of the phosphor of the present invention is represented by a solid line, and the composition formula is C a 1. 9 7 S i 5 Ν 8: EUG. 0 3 Spectrum to

The dotted line indicates. [Table 4] Excitation wavelength spike intensity Peak wavelength chromaticity X y Ca〇.985AlSiN3: EU0.015 460nm 137.4% 656. 2 0. 671 0. 327 Cai. 9? Si δNβ: Eu〇. 03 460nm 100. 0% 609 · 2 0. 593 0.405 312XP / Invention Specification (Supplement) / 94-06 / 94105848 32

200536152 Tian Hui I ϋ and the results in Table 4 show that the phosphor of the present invention has a compositional formula C a 1,9 7 S 1 5 Ν 8: E u. .. 3 After comparing the phosphors, the peak intensity is about 40% higher, which is a very efficient phosphor. Particularly preferred is that the compositional Cai 97Sl5N8: Eu ° phosphor has a peak wavelength near 610 nm and is considered orange. In contrast, since the phosphor of the present invention has a peak wavelength near 65 6 nm, it will be closer to red. Therefore, when other LEDs are combined to produce white LEDs, the mixing ratio of red phosphors can be reduced. (Example 5) Commercially available Ca3N2 (2N), A1N (3N), SiK3N), Eu2〇3 (3N), and Ca3N2: 0.985 / 3mol, AlN: 1mol, Si3N4: 1 / 3mol, Eu 2 03: 〇. 〇i 5/2 mo 1 method, after weighing each raw material separately, use a mortar to mix in a glove box under a nitrogen environment. The mixed powder raw materials were charged into a hanging pin and subjected to a pressure of 1,600 in a nitrogen atmosphere at a pressure of 0.05 MPa. It was calcined at 3 ° C for 3 hours, and then changed from 16,000 in 1 hour. 〇Cooling to 20 〇t, will be paid to contain the composition (^ .. 985 people 18 丨 0 .. 23 ~ 2.985: £ 11... 15 as shown in the formation phase of the photogenic body.

The particle size of the obtained phosphor sample was 3 to 4 // m. (The particle diameters of the obtained phosphors are also 3 to 4 // m in the following Examples 6 to 10.) The obtained phosphors were irradiated with an excitation light source at a wavelength of 460 n in, and the emission characteristics were measured. The luminous intensity is defined as 100% according to the luminous intensity of the phosphor in Example 6 described later; the luminous intensity is determined according to the calculation method of the X γ z color system regulated by JISZ 8 701, and Y 値 is calculated. The brightness of the 6 phosphor is set to 100%; the chromaticity is obtained by calculating the chromaticity X, y according to the calculation method specified in JISZ 787. In addition, the concentration of oxygen and nitrogen (0 / N) in the phosphor particle sample was measured using an oxygen and nitrogen simultaneous analysis device (τ C-4 3 6) made by LEC 0, 33 312XP / Invention Specification (Supplementary Pieces) / 94-06 / 94105848 200536152 The concentration of other elements is measured using ICP. Table 5 shows the raw material composition formula of this phosphor, the results of the concentration analysis of each element, and the results of the measurement of the luminescence characteristics. Next, the results of comparing the powder X-ray diffraction pattern of this phosphor sample with the peaks of the J C P D S card are shown in FIGS. 1 (A) and (B).

From Figs. 1 (A) and (B), it is known that the crystal structure of the phosphor in Example 5 is as described in the embodiment, and the C a A 1 S i N 3 crystal and X-ray diffraction pattern described in the JCPDS card are described. The overall pattern of the main spikes is similar. However, it is judged that the crystal structure of the two will have a crystal structure with a different crystal plane interval due to the difference in the amount of all the oxygen in the structure and a part of Ca will be replaced with Eu. In particular, it can be judged that the formation phase of the phosphor of the present invention also has the same orthorhombic crystal as the CaAlSiN3 crystal described in the J C P D S card. In addition, the main peak in the X-ray diffraction pattern of the phosphor-generating phase in the related example 5 is also as described in the embodiment, and the Bragg angle (20) is 36.5. ~ 37.5 °, 40.9. ~ 41.9. , 41.9. ~ 42.9. , 5 6 · 3 0 to 5 7 · 3 ϋ, 6 6 · 0. ~ 6 7 · 0 0, 7 5 · 8 0 ~ 7 6. 8 0 and 8 1 · 0 0 ~ 8 3 · 0 0 have characteristic spikes, especially at 3 6 .5 ° ~ 3 7. 5 The peaks in the range of °, 41.9 ° to 42.9 ° are characteristic peaks with extremely strong intensity, and the peaks in the range of 56.3 ° to 57.3 ° are second only to the characteristic peaks. . These spikes belong to diffraction spikes having a relative intensity of more than 10% when the relative intensity of the strongest diffraction peak in the X-ray diffraction pattern is set to 100%. Furthermore, from the viewpoint of the half-value width of the diffraction pattern, the sharp peaks will obtain sharp diffraction peaks with half-value widths below 0.2 °. The sharp diffraction tip + indicates that the non-formation phase is not an amorphous structure 'but has a structure with superior crystallinity 34 312XP / Invention Specification (Supplement) / 94-06 / 94105848 200536152. As a result of measuring the oxygen and nitrogen concentration, the analysis of oxygen concentration and nitrogen concentration in the phosphor sample was 2.4 wt% and 28.5 wt%. In addition, the oxygen concentration calculated from the raw material loading amount of the phosphor sample was 0.3 wt%, and the nitrogen concentration was 30 wt%. If the two are compared, the relevant oxygen concentration is relative to the oxygen in the generated phase. The concentration of 0.3 wt ° / 〇, will contain considerable oxygen in the sample. The extra about 2 wt% of oxygen can be judged to be the oxygen that adheres to the surface of the raw material at the beginning, the oxygen mixed in due to the oxidation of the surface of the raw material during firing or firing, and the adsorbed to Yingguang after firing Oxygen on the sample surface! It can be considered that there exists oxygen other than the generated phase structure. On the other hand, the relevant nitrogen concentration was 28.5 wt ° / 0 with respect to the nitrogen concentration in the formation phase, and the sample contained almost the same amount of nitrogen (30 wt%). From this result, it can be judged that there is almost no additional nitrogen other than the generated phase structure. In addition, the excitation spectrum showing the excitation band of the obtained phosphor sample and the emission spectrum showing the emission characteristics were measured. The results are shown in Figs. 2 and 3.

The vertical axis of Fig. 2 is the relative intensity, and the horizontal axis is the excitation wavelength (n m). The excitation spectrum measured according to the excitation wavelength of 65.6.2 n m will be plotted according to the solid line. From the measurement results in FIG. 2, it is known that the excitation spectrum of the phosphor sample of Example 5 spans a wide range of 250 nm to 6 0 n in, and it is determined that the wavelength of 3 0 0 n in to 5 can be fully utilized. 50 n in ultraviolet light to a wide range of visible light. The vertical axis of the system shown in Figure 3 is the relative intensity, and the horizontal axis is the emission wavelength (nm). The emission spectrum when the excitation light is excited at a wavelength of 4 60 n in, is 35 312XP / Invention Specification (Supplement) according to the solid line. / 94-06 / 94105848 200536152 The drawing of points. It is known from the measurement results in Fig. 3 that the emission spectrum of the phosphor sample of Example 5 has a peak ridge at 6 5 4 n m and a wide half-value width. (Example 6) The mixed raw materials were charged into a crucible, and held at 150 ° C for 3 hours in a nitrogen environment to perform firing, and then cooled from 15,000 ° C in 1 hour. At 200 ° C, except that phosphors containing the phase represented by the composition Ca.985AlSi〇Q. () 23N2.985: Eu.015 () were obtained, the phosphors of Example 6 were obtained as in Example 5. • Phosphor. Table 5 lists the measurement results of the raw material composition formula, the oxygen and nitrogen concentration, and the luminous characteristics of the phosphor sample, and the powder X-ray diffraction pattern of the obtained phosphor is plotted in FIG. 4 by a thick solid line. -A to G.

Figure 4-A shows the X-ray diffraction pattern of the Bragg angle (20) across the full range of 0 ° ~ 90 °, and Figure 4-B ~ G is an enlarged view of the characteristic part of the Bragg angle. The system shown in Fig. 4-B is 35 ° ~ 40 °, the system shown in Fig. 4-C is 40 ° ~ 45 °, the system shown in Fig. 4-D is 55 ° to 60 °, and the system shown in Fig. 4-E is 65 ° to 70 ° , Figure 4-F series 7 5 ° ~ 80 0 °, Figure 4-G series 80 ° ~ 8 5 ° range. In addition, for convenience of description, the vertical axes of the powder X-ray diffraction patterns of Examples 6 to 10 in FIGS. 4_A to G are depicted as being offset from each other by 100 c ps. (Example 7) In the mixing ratio of each raw material, except that Caa N 2 was set to (0 · 9 8 5-0.2 5) / 3 m〇1, and Ca 0 was set to 0.2 5 ιη ο On the 1st day, the rest were prepared in the same manner as in Example 6, and the light emission characteristics were measured. The measurement results of the raw material composition formula, oxygen and nitrogen concentration, and luminescence characteristics of this phosphor sample are listed in Table 5 of 36 312XP / Invention Specification (Supplement) / 94-06 / 94105848 200536152. The powder X-ray diffraction pattern is depicted in Figure 4-A to G as a thin solid line. (Example 8)

In terms of the mixing ratio of each raw material, in addition to setting Ca 3 N 2 to (0.985-0.50) / 3 m〇1, and setting Ca 0 to 0.50 m〇1 In the rest, a phosphor sample was prepared as in Example 6, and the luminescence characteristics were measured. Table 5 lists the measurement results of the raw material composition formula, oxygen and nitrogen concentration, and luminescence characteristics of the phosphor sample, and the powder X-ray diffraction pattern of the obtained phosphor is depicted in FIG. 4-A as a thick dotted line. ~ G. (Example 9) Except for the mixing ratio of each raw material, Ca 3 N 2 was set to (0.98 5-0.75) / 3 m ο 1 and Ca 0 was set to 0.75 m. ο On the 1st day, the rest were prepared as in Example 6 and the light emission characteristics were measured. Table 5 lists the measurement results of the raw material composition formula, the oxygen and nitrogen concentration, and the luminous characteristics of the phosphor sample, and the powder X-ray diffraction pattern of the obtained phosphor is depicted in FIG. 4-A by a thin dotted line ~ G. (Example 10) A phosphor sample was prepared in the same manner as in Example 6 except that C a 0 was set to 0.98 5 m ο 1 in terms of the mixing ratio of each raw material, and was the same as in Example. 5 general measurement of luminous characteristics. Table 5 lists the measurement results of the raw material composition formula, the oxygen and nitrogen concentration, and the luminous characteristics of the phosphor sample, and the powder X-ray diffraction pattern of the obtained phosphor is depicted in FIG. 4 by a thick single-dotted dotted line. -0 to A ~ G [Table 5] 37 312XP / Invention Specification (Supplement) / 94-06 / 94105848 200536152 Filling formula of raw material Oxygen and nitrogen concentration peak wavelength (nm) Luminous intensity (%) Chroma luminance (%) 〇 (wt%) N (wt%) X y Example 5 Ca 0.098δA 1S i 〇0.023N2.985: Elio. 0150 2.2 27.5 656.2 115.0 0. 679 0. 320 104 · 8 Example 6 Ca 0. 985A1S i 〇0.023N2.985: Elio. 0150 2.4 28.5 654.0 100.0 0.675 0. 324 100.0 Example 7 Ca0. 98δΑ 1S i 〇0.273N2.818: Elio. 0I50 5.2 25.1 646.1 69.7 0.649 0.350 102.6 Example 8 Ca. 98δΑ 1S i Oo. 523N2.652: Euo. 0150 7.3 21.1 637.5 40.7 0.599 0.398 105.1 Example 9 Ca0. 98δΑ 1S i Oo. 773N2.485: Elio. 0150 9.0 21.0 624.5 30.8 0. 571 0.426 102.0 Example 10 Ca 〇8δΑ 1S i 〇8N2.328: Elio. 0150 11.3 20.7 611.0 22.4 0.540 0.451 98.4 (Related Example 6 Study 0 1) 1) of the phosphor of oxygen, nitrogen concentration

From Example 6 to Example 10, the mixing ratio of Ca 3 N 2 and Ca 0 in the raw materials was changed, and the oxygen loading was increased, so the analysis of oxygen concentration in the phosphor will also increase. Moreover, the oxygen concentration in the phosphor will be greater than the weight% 値 calculated from the oxygen loading. This phenomenon is considered to be caused by the fact that in the phosphors of Examples 6 to 10, oxygen is not only contained in the phosphor structure, but also adsorbed on the surfaces of the phosphor particles. On the other hand, related nitrogen concentration analysis 値, in terms of nitrogen loading, almost the same amount of nitrogen was contained in the sample. From this result, it can be judged that the reason is that there is almost no nitrogen in addition to the generated phase structure, and the nitrogen is contained in the phosphor structure. 2.) The relationship between the oxygen concentration in the phosphor and the X-ray diffraction pattern. It is known that the luminous intensity of the phosphor will gradually decrease from Example 6 to Example 10. Therefore, when the luminous intensity of Example 6 is set to a relative intensity of 100%, the phosphor of Example 7 has a relative intensity of about 70%, while that of Examples 8 to 10 is less than 40%. The relationship between the amount of oxygen contained in the phosphor structures of Examples 6 to 10 and the X-ray diffraction pattern will be described with reference to Figs. 4-A to G. From Figure 4-A ~ G, as the amount of oxygen in the phosphor increases, it will be at 36.5 ° ~ 38 3 12XP / Invention Manual (Supplement) / 94-06 / 94105848

200536152 37.5ϋ, 41.9. ~ 42. 9. The peak of the range is the beginning, 40 • 9. ~ 41 · 9〇56 · 3ϋ ~ 57.3 '66. 0 ° ~ 67.0, 75 · 80 ~ 76 · 80, and 81. 0 ° -83 Bragg angles of characteristic spikes (2 0) The Ca A 1 S i N 3 described in the above JCPDS card is crystallized toward the high-angle side. However, as the amount of oxygen in the light body increases, the intensity of X-ray diffraction peaks will gradually increase, so it is judged that the crystallinity will gradually decrease. This phenomenon can be considered to be caused by the gradual change of the crystal structure of the phosphor as the amount of oxygen contained in the phosphor structure increases. In addition, in Example 8, Example 9, and Example 1, when Ca 0 was filled to 0 · 50 m ο 1 and the amount of oxygen was increased, it was judged that the luminescence was due to the formation of an impure phase or residual reaction raw materials. The intensity will decrease. Therefore, from the viewpoint of obtaining a phosphor with a higher luminous intensity, when the relative intensity of the strongest peak in the powder X-ray diffraction pattern generated by C rays is set to 100%, the relative intensity is 10%. The Bragg angle (20) of the main spikes of the above shot spikes will be in the range of 36.5 ° to 37. 41.9 ° to 42.9 °, and the characteristic peaks of the next order will be 56.3 ° to 5 °. 7.3 ° Fan and the first-level characteristic peaks are at 40.9 ° ~ 4 1 · 9 °, 66.0 ° ~ 6 7.0 °, 75.8 ° ~ 76.8 ° and 8 1 The bodies shown in Examples 6 and 7 in the range of 0 ° to 83.0 ° will belong to the preferred phosphors. 3.) The interception between the oxygen concentration in the phosphor and the peak wavelength of the light emission wavelength shows that the example is from 6 to 10, and the peak wave of the light emission wavelength of the phosphor gradually changes from 6 5 4 nm to 6 1 1 η m. shorten. 4.) The relationship between the oxygen concentration in the phosphor and the luminous brightness

In Examples 6 to 10, it was learned that the phosphor brightness of each example was more than 312XP / Invention Specification (Supplement) / 94-06 / 94105 848, and then the fluorescence was weak, and the fluorescence remained as above. Diffraction around 5. In the surrounding area, the fluorescent length is almost 39 200536152 to a certain state. This phenomenon can be judged as following Example 6 towards 10, the luminous intensity of the phosphor will gradually decrease. In contrast, the peak wavelength of the luminescence will also decrease, and it will enter the region with higher human visual sensitivity, thereby the brightness will be almost The display must be 値. 5.) The relationship between the oxygen concentration in the phosphor and the light-emitting chromaticity In Examples 6 to 10, it is known that the light-emitting chromaticity X of each of the phosphors of the embodiments is 0.5 to 0.7. The degree y is an optimal range of 0.3 to 0.5. (Comparative Example 1)

The C a 2 S i 5 N 8: E u phosphor was modulated in accordance with the aforementioned Patent Documents 4 and 5, and the X-ray diffraction pattern was measured. This measurement result is shown in Figure 5. The X-ray diffraction peaks obtained in FIG. 5 are compared with those disclosed in Patent Document 4 (S c h 1 i e p e r a n d

Schlick: Nitridosilicate I, Hochtemperatursynthese und Kristal lstruktur von C a 2 S i 5 N 8, Z. anorg. Al lg. Che. 6 2 1, (1 9 9 5), p. 1 0 3 7) As a result of comparison, it was confirmed that the phosphor is a Ca 2 S i 5 N 8: E u phosphor disclosed in Patent Documents 4 and 5. The crystal system of the phosphor is monoclinic, which is completely different from the phosphor of the present invention.

(Comparative Example 2) An α-silicon phosphor was modulated according to the above-mentioned Patent Document 3, and an X-ray diffraction pattern was measured. The term "α-silon" refers to an oxynitride-based ceramic composed of a nitride and an oxide. It is composed of 4 elements such as Shi Xi, Ming, oxygen, and nitrogen. The i position is replaced by A 1 and the N position is replaced by 0 and the solution is solid solution, and a (Si, Al) (0, N) 4 tetrahedron is used as a skeleton, and the solution is different from that of Cold-Shi Xilong. Structure of metal M (M: a lanthanoid metal other than Li, Mg, Ca, Y, La 40 312XP / Invention Specification (Supplement) / 94-06 / 94105848 200536152 and Ce, 0 < x S 2). As a result, the X-ray diffraction peaks of the α-silon phosphor showed a diffraction pattern similar to the X-ray diffraction peaks of a-S i 3 Ν 4. The measurement results are shown in Figure 6. The X-ray diffraction spike shown in FIG. 6 is a pattern similar to a-S i 3 N 4. Here, it is compared with the silicon dragon diffraction pattern reported by JCPDS. As a result, the X-ray diffraction peaks are consistent, and it can be confirmed that the conventional technology of the fluorescent system shown in FIG. 6 is disclosed in α-silicon phosphor disclosed in Patent Document 3. . The crystal system of α-silon is hexagonal, which also belongs to a structure completely different from the phosphor of the present invention.

(Example 11) Commercially available Ca3N2 (2N), A1N (3N), Si3N4 (3N), and Eu2〇3 (3N) were prepared, and the molar ratio of each element was Ca: Al: Si: Eu = 0.985 : 1: 1: 0. 015 method to weigh each raw material, and use a mortar to mix in a glove box under a nitrogen environment. The mixed raw materials were filled into a crucible made of boron nitride, and the temperature was raised to 15 0 ° C at a temperature increase rate of 15 ° C / mi η in a nitrogen environment at a pressure of 0.05 MPa. Then, it was fired after being held in 150 ° C. for 3 hours, and then cooled from 150 ° C. to 200 ° C. within 1 hour to obtain a phosphor having a composition formula Ca.985SiAlN3: Euu15. The obtained phosphor powder was irradiated with monochromatic light of 4 60 nm, and the result is shown in FIG. 1 1, which shows red light emission with a peak of light emission at 6 5 6 nm. In addition, the impurity carbon obtained by chemical analysis The concentration and the impurity oxygen concentration were 0.043% by weight and 2.09% by weight, respectively. (Comparative Example 3) The vessel used for firing was changed from a crucible made of boron nitride to a crucible made of carbon. Except for the rest, the phosphor was produced under the same conditions as in Example 11. After 41 312XP / Invention Specification (Supplement) / 94-06 / 94105848 200536152, the phosphor powder obtained was irradiated with 4 60 nm monochromatic light. , It shows a red light emission with a light emission peak at 650 nm. Figure 11 shows the relative luminous intensity and chemical conversion of the phosphor prepared in this comparative example. Analysis of the carbon concentration and impurity oxygen concentration was not obtained pure.

As shown in FIG. 11 and FIG. 12, the phosphor obtained by using a crucible made of carbon for the firing container is compared with the phosphor produced in Example 1 by using a crucible made of boron nitride. As a result, the luminous intensity was reduced by about 26%. The phosphor produced by using a carbon crucible will increase the amount of carbon in the impurities to 0.80% by weight. Therefore, it is judged that the carbon in the impurities causes a decrease in luminous intensity. (Comparative Example 4) A phosphor was produced under the same conditions as in Example 11 except that the container used for firing was changed from a crucible made of boron nitride to a crucible made of alumina. The obtained phosphor powder was irradiated with a monochromatic light of 460 nm, and the result showed a red light emission with a luminescent peak at 652 nm. Figure 11 shows the relative luminous intensity of the phosphor prepared in this comparative example and the carbon concentration and the oxygen concentration of the impurities obtained by chemical analysis. As shown in Fig. 11 and Fig. 12, the phosphor obtained by using a crucible made of alumina as the firing container is lower than the phosphor of Example 1 obtained by using a crucible made of boron nitride. The result that the luminous intensity is reduced by about 20% will be obtained. The phosphor produced by using an aluminum oxide crucible will increase the amount of impurity oxygen to 3.02% by weight. Therefore, it is judged that the impurity oxygen will cause a decrease in luminous intensity. The present invention has been described based on the embodiments described above, but the present invention is not limited to this. [Schematic description] 42 312XP / Invention Specification (Supplement) / 94-06 / 94105848 200536152 Figures 1 (A) and (B) are powder X-ray diffraction patterns of the main generated phase of the phosphor of the present invention and the X The ray diffraction pattern is compared with the spikes of the JCPDS card. Fig. 2 is an excitation spectrum diagram of the main generated phase of the phosphor of the present invention. FIG. 3 is a light emission spectrum chart of the main generated phase of the phosphor of the present invention. Figure 4-A shows the powder X-ray diffraction pattern of the phosphors in the main generation phase of Examples 6 to 10 of the present invention. Figure 4-B shows the powder X-ray diffraction pattern of the phosphors in the main generation phase of Examples 6 to 10 of the present invention.

Figure 4-C shows the powder X-ray diffraction pattern of the phosphors in the main generation phase of Examples 6 to 10 of the present invention. Fig. 4-D shows the powder X-ray diffraction pattern of the main phase of the phosphors in Examples 6 to 10 of the present invention. Fig. 4-E shows the powder X-ray diffraction pattern of the main phase of the phosphors in Examples 6 to 10 of the present invention. Figure 4-F shows the powder X-ray diffraction pattern of the phosphors in the main generation phase of Examples 6 to 10 of the present invention. Figure 4-G is a powder X-ray diffraction pattern of the phosphors in the main generation phase of Examples 6 to 10 of the present invention. FIG. 5 is an X-ray diffraction pattern of a conventional phosphor of a comparative example. FIG. 6 is an X-ray diffraction pattern of a conventional phosphor of a comparative example. FIG. 7 is a light emission spectrum chart of a phosphor of the present invention. FIG. 8 is an excitation spectrum diagram of a phosphor of the present invention. Fig. 9 is a graph showing the composition and luminous intensity of the phosphor of the present invention. FIG. 10 is a light emission spectrum chart of the phosphor of the present invention and the conventional technology. 43 312XP / Invention Specification (Supplement) / 94-06 / 94105848 200536152 Fig. 1 1 shows the material of the firing container (crucible) used in the manufacture of the phosphor of the present invention, the characteristics of the produced phosphor and the concentration of impurities. table. Fig. 12 is a graph showing the relationship between the material of a firing container (crucible) used for firing and manufacturing the C a A 1 S 1 N 3 phosphor of the present invention and the above-mentioned phosphor luminous intensity.

44 312XP / Invention Specification (Supplement) / 94-06 / 94105848

Claims (1)

200536152 10. Scope of patent application: 1. A phosphor, represented by the composition formula M m A a B b N n: Z z; characterized in that, in the above phosphor, the M element is valence Π Element, element A with valence number m, element B with valence number IV, N-based nitrogen, Z-based activator, (m + z): a: b: η = 1: 1: 1 : 3. 2. The phosphor according to item 1 of the patent application scope, wherein the M element is at least one selected from Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg. Element; A element is at least one element selected from B (Shi Peng), Al, Ga, In, Tl, Y, Sc, P, As, Sb, Bi; element B is selected from Si, Ge, At least one element is selected from Sn, Ti, Hf, Mo, W, Cr, Pb, and Zr; the Z element is at least one element selected from a rare earth element or a transition metal element. 3. If the phosphor of item 1 or 2 of the patent application scope, wherein A element 4. For the phosphor of any one of the items 1 to 3 of the scope of patent application, wherein the mother structure of the above phosphor does not contain oxygen. 5. The phosphor according to any one of claims 1 to 4, in which the molar ratio of the M element to the activator Z element: z / (m + z) 値, is 0. 0 0 0 1 or more and 0.5 or less. 6. The phosphor according to any one of claims 1 to 5, wherein the M element is at least one selected from Mg, Ca, Sr, Ba, Zη 45 45 312XP / invention Elements of Instructions (Supplements) / 94-06 / 94105848 200536152. 7. The phosphor according to any one of claims 1 to 6, wherein the Z element is at least one element selected from Eu, Mn, and Ce. 8. The phosphor according to item 7 of the patent application scope, wherein the Z element is Eu. 9. The phosphor according to item 8 of the scope of patent application, wherein the M element is Ca. 10. The phosphor according to any one of claims 1 to 9 of the scope of patent application, wherein the above fluorescent system is in the form of a powder. 1 1. The phosphor according to item 10 of the scope of patent application, wherein the average particle size of the phosphor is below 20 // m and above 1 // Π1. 12. The phosphor according to any one of claims 1 to 11 in the scope of patent application, which contains: the strongest diffraction peak in the powder X-ray diffraction pattern obtained by using C ο K (2 rays) When the relative intensity is set to 100%, the Bragg angle (20) of the X-ray diffraction pattern is in the range of 36.5 ° to 37.5 ° and 41.9 ° to 42.9 °. Within, the phase containing diffraction peaks showing a relative intensity of more than 10% is used as the main generated phase. 1 3. As the phosphor of any one of the items 1 to 11 in the scope of patent application, which contains: When will When the relative intensity of the strongest diffraction peak in the powder X-ray diffraction pattern obtained by using C ο α rays is set to 100%, the Bragg angle (2 0) of the X-ray diffraction pattern is 36. 5 ° ~ 3 7 · 5 °, 4 1 .9 ° ~ 4 2. 9 ° and 5 6 · 3 ° ~ 5 7. 3 °, including phases with diffraction peaks showing a relative intensity of 10% or more As the main generating phase. 14. The phosphor according to any one of claims 1 to 11 in the scope of patent application, which contains: powder X-rays to be obtained by using C ο α rays When the relative intensity of the strongest diffraction peak in the diffraction pattern is set to 100%, 46 312XP / Invention Specification (Supplement) / 94-06 / 94105848 200536152 The Bragg angle (2 0) of the X-ray diffraction pattern is at 3 6 · 5 ° ~ 37.5 °, 40.9〇 ~ 41.90, 41.9. ~ 42.90, 56.30 ~ 57.30, 66.0 ° ~ 67.0〇, 75.8 ° ~ 76.8 °, and 81.0 ° ~ In the range of 83.0 °, the phase containing diffraction peaks showing a relative intensity of more than 10% is used as the main generated phase. 15. Fluorescence such as any of the items 12 to 14 in the scope of patent application 0 8 重量。 The body, wherein the crystal phase of the above-mentioned generated phase is orthorhombic. 1 6. The phosphor according to any one of claims 1 to 11 in the scope of patent application, wherein the carbon content is less than 0.08 weight %. 1 7. The phosphor according to any one of claims 1 to 11 in the scope of patent application, wherein the oxygen content is less than 3.0% by weight. 1 8. The phosphor according to any one of claims 1 to 11 in the scope of patent application, wherein the carbon content is less than 0.8 wt% and the oxygen content is less than 3.0 wt%. 19. A light source characterized by having a phosphor according to any one of claims 1 to 18 and a light-emitting portion emitting light of a first wavelength; using a part of the light of the first wavelength as an excitation source, The phosphor is caused to emit light at a wavelength different from the first wavelength. 20. The light source according to item 19 of the scope of patent application, wherein the light-emitting part emitting light of the first wavelength is an LED. 2 1. The light source according to item 19 or 20 of the patent application scope, wherein the first wavelength is a wavelength of 300 nm to 550 nm. 2 2. — An LED having the features of a phosphor according to any one of claims 1 to 18 and a light-emitting portion that emits light of a first wavelength; and a part of the light of the first wavelength is regarded as The excitation source causes the above-mentioned fluorescent 47 312XP / Invention Specification (Supplement) / 94-06 / 94105848 200536152 to emit light at a wavelength different from the first wavelength. 2 3. According to the LED of item 22 of the patent application scope, wherein the first wavelength is a wavelength of 3 0 0 m to 5 5 0 m. 24. — A method for manufacturing a nitride phosphor, which is used to manufacture a nitride phosphor according to any one of claims 1 to 18 in the scope of patent application; characterized in that the above-mentioned nitride phosphor is Raw materials are filled in a firing container made of boron nitride, and firing is performed in an inactive environment to obtain a nitride phosphor. 25. According to the φ method for manufacturing a nitride phosphor according to item 24 of the scope of patent application, wherein the above-mentioned nitride phosphor raw material is carried out at a temperature of 1 2 0 ° C ~ 1 7 0 ° C Sintered. 2 6. The method for manufacturing a nitride phosphor according to item 24 or 25 of the scope of application for a patent, wherein, when the above-mentioned nitride phosphor raw material is fired, the content is 0.5 M Pa or less. Baking is performed under pressure. 48 312XP / Invention Specification (Supplement) / 94-06 / 94105848